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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2026

Genomic signatures in Variovorax enabling colonization of the Populus endosphere

Microbial colonization of plant roots involves strong selective pressures that shape the structure and function of root-associated communities. In particular, the endosphere represents a highly selective environment requiring host entry and in planta persistence. However, strain-specific microbial traits that enable endosphere colonization remain poorly understood. Here, we use a defined, genome-resolved community of 28 Variovorax strains isolated from the roots of Populus deltoides and Populus trichocarpa (poplar trees) to determine which strains partition between rhizosphere and endosphere compartments and to identify the genomic traits associated with endosphere specialization. By combining strain-resolved metagenomic profiling, comparative genomics, and functional assays, we demonstrate that dominant endosphere colonizers are enriched in genes related to nutrient metabolism, redox balance, transcriptional regulation, and a conserved L-fucose utilization pathway experimentally shown to enhance root colonization. Not all strains succeed through the same strategy. Community-wide functional profiling revealed a distinct and reduced set of traits in the endosphere, including orthogroups associated with low-abundance strains that were overlooked in strain-level analyses. These findings reveal that multiple ecological strategies, such as metabolic competition, regulatory adaptation, and niche specialization, can support endosphere colonization. Our results advance the understanding of how bacterial colonization traits are distributed and deployed within a plant microbiome and suggest that host filtering selects for distinct, and sometimes complementary, microbial strategies. This work supports a shift toward mechanistic, genome-resolved models of microbiome assembly and offers a framework for linking microbial function to host colonization success.

comparative genomics↗
DOE OSTI2023

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Evaluating CO 2 mitigation strategies in SAF biorefineries: Techno-economic and life cycle analysis

The aviation sector requires scalable decarbonization strategies, and lignocellulosic sustainable aviation fuel (SAF) represents a promising pathway. This study comparatively evaluates the techno-economic analysis and life cycle assessment (LCA) of three CO 2 management strategies integrated within a U.S.-based gasification–Fischer–Tropsch SAF biorefinery: (i) catalytic hydrogenation of captured CO 2 to methanol, (ii) geological CO 2 sequestration, and (iii) mineralization to sodium bicarbonate (NaHCO 3 ). Techno-economic analysis indicates that methanol synthesis requires approximately 26% higher capital investment and 33% higher operating costs than mineralization. Although methanol co-production generates the highest gross revenue, NaHCO 3 production reduces the SAF minimum selling price by approximately 38% relative to both methanol synthesis and geological sequestration pathways, reflecting a more balanced cost allocation through mineral co-product valorization. Geological sequestration lowers operating costs by nearly 50% compared with methanol synthesis but remains highly dependent on carbon credit mechanisms. LCA reveals substantial divergence in climate performance. Relative to methanol synthesis, sequestration improves net greenhouse gas performance by approximately 163%, transitioning the system from net-positive to net-negative emissions. Mineralization further enhances carbon mitigation, achieving roughly 85% greater carbon reduction than sequestration and over sixfold improvement relative to methanol synthesis within the defined system boundary. Sensitivity analysis identified hydrogen price, co-product market value, and process emissions as dominant drivers. Under baseline assumptions, CO 2 mineralization is found to offer the most balanced pathway.

Carbon capture and storage↗
DOE OSTI2021

Saturation physics of threshold heat-flux reduction

The saturation physics of ion-temperature-gradient-driven turbulence is examined in relation to the temperature-gradient variation of the heat flux, which can exhibit an upshift of the critical gradient for significant flux relative to the linear instability threshold. Gyrokinetic measurements of saturation properties and spectral energy transfer, which will be defined in Sec. II, are presented, indicating that the physics of saturation is fundamentally unchanged on either side of the upshifted gradient. To analyze heat transport below and above the upshifted critical gradient, a fluid model for toroidal ion-temperature-gradient turbulence is modified to include the kinetic instability threshold. The model and the heat flux are rendered in the eigenmode decomposition to track the dominant mode-coupling channel of zonal-flow-catalyzed transfer to a conjugate stable mode. Given linear and nonlinear symmetries, the stable mode level and the cross-correlation of the unstable and stable mode amplitudes are related to the unstable mode level via linear physics. Here, the heat flux can then be written in terms of the unstable-mode level, which through a nonlinear balance depends on the eigenmode-dependent coupling coefficients and the triplet correlation time of the dominant coupled modes. Resonance in these quantities leads to suppressed heat flux above the linear threshold, with a nonlinear upshift of the critical gradient set by the resonance broadening of a finite perpendicular wavenumber and collisionality.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Impact of biomass burning aerosols on radiation, clouds, and precipitation over the Amazon: relative importance of aerosol–cloud and aerosol–radiation interactions

Biomass burning (BB) aerosols can influence regional and global climate through interactions with radiation, clouds, and precipitation. Here, we investigate the impact of BB aerosols on the energy balance and hydrological cycle over the Amazon Basin during the dry season. We performed simulations with a fully coupled meteorology–chemistry model, the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), for a range of different BB emission scenarios to explore and characterize nonlinear effects and individual contributions from aerosol–radiation interactions (ARIs) and aerosol–cloud interactions (ACIs). The ARIs of BB aerosols tend to suppress low-level liquid clouds by local warming and increased evaporation and to facilitate the formation of high-level ice clouds by enhancing updrafts and condensation at high altitudes. In contrast, the ACIs of BB aerosol particles tend to enhance the formation and lifetime of low-level liquid clouds by providing more cloud condensation nuclei (CCN) and to suppress the formation of high-level ice clouds by reducing updrafts and condensable water vapor at high altitudes (>8 km). For scenarios representing the lower and upper limits of BB emission estimates for recent years (2002–2016), we obtained total regional BB aerosol radiative forcings of –0.2 and 1.5 W m –2 , respectively, showing that the influence of BB aerosols on the regional energy balance can range from modest cooling to strong warming. We find that ACIs dominate at low BB emission rates and low aerosol optical depth (AOD), leading to an increased cloud liquid water path (LWP) and negative radiative forcing, whereas ARIs dominate at high BB emission rates and high AOD, leading to a reduction of LWP and positive radiative forcing. In all scenarios, BB aerosols led to a decrease in the frequency of occurrence and rate of precipitation, caused primarily by ACI effects at low aerosol loading and by ARI effects at high aerosol loading. The dependence of precipitation reduction on BB aerosol loading is greater in a strong convective regime than under weakly convective conditions. Overall, our results show that ACIs tend to saturate at high aerosol loading, whereas the strength of ARIs continues to increase and plays a more important role in highly polluted episodes and regions. This should hold not only for BB aerosols over the Amazon, but also for other light-absorbing aerosols such as fossil fuel combustion aerosols in industrialized and densely populated areas. The importance of ARIs at high aerosol loading highlights the need for accurately characterizing aerosol optical properties in the investigation of aerosol effects on clouds, precipitation, and climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Self-adaptive weights based on balanced residual decay rate for physics-informed neural networks and deep operator networks

Physics-informed deep learning has emerged as a promising alternative for solving partial differential equations. However, for complex problems, training these networks can still be challenging, often resulting in unsatisfactory accuracy and efficiency. In this work, we demonstrate that the failure of plain physics-informed neural networks arises from the significant discrepancy in the convergence rate of residuals at different training points, where the slowest convergence rate dominates the overall solution convergence. Based on these observations, we propose a pointwise adaptive weighting method that balances the residual decay rate across different training points. The performance of our proposed adaptive weighting method is compared with current state-of-the-art adaptive weighting methods on benchmark problems for both physics-informed neural networks and physics-informed deep operator networks. In conclusion, through extensive numerical results we demonstrate that our proposed approach of balanced residual decay rates offers several advantages, including bounded weights, high prediction accuracy, fast convergence rate, low training uncertainty, low computational cost, and ease of hyperparameter tuning.

Balanced convergence rate↗
DOE OSTI2026

Virtual Growth of SRF Materials

Niobium's native surface oxide affects SRF cavity and superconducting qubit performance, motivating interest in controlling its crystalline structure. We combine a literature-derived machine-learning analysis with temperature-dependent XRD to study crystalline ordering in Nb2O5. Random Forest models, trained on 74 processing conditions from 17 papers and validated by leave-one-group-out cross-validation, predicted broad crystallinity outcomes well (balanced accuracy 0.809), but struggled with specific polymorph identity (0.577). Annealing temperature was the dominant predictor across all targets; oxygen partial pressure showed negligible importance, reflecting narrow literature coverage rather than physical irrelevance. Temperature-dependent XRD on anodized and H2O2-treated Niobium showed structural evolution consistent with the machine learning predictions. Our model and overall approach provide a data-driven framework for identifying and optimizing conditions that promote crystallization in initially amorphous oxides. This framework can guide the selection of growth and post-annealing conditions for Nb surfaces by narrowing the experimental parameter space, thereby reducing trial-and-error efforts in developing oxide structures relevant to SRF applications.

Tilkin, Anthony [Fermilab]↗
DOE OSTI2026

Virtual Growth of SRF Materials: A Machine Learning Approach to Predict the Crystalline Structural Ordering in Nb Surface Oxides

Niobium's native surface oxide affects SRF cavity and superconducting qubit performance, motivating interest in controlling its crystalline structure. We combine a literature-derived machine-learning analysis with temperature-dependent XRD to study crystalline ordering in Nb2O5. Random Forest models, trained on 74 processing conditions from 17 papers and validated by leave-one-group-out cross-validation, predicted broad crystallinity outcomes well (balanced accuracy 0.809), but struggled with specific polymorph identity (0.577). Annealing temperature was the dominant predictor across all targets; oxygen partial pressure showed negligible importance, reflecting narrow literature coverage rather than physical irrelevance. Temperature-dependent XRD on anodized and H2O2-treated Niobium showed structural evolution consistent with the machine learning predictions. Our model and overall approach provide a data-driven framework for identifying and optimizing conditions that promote crystallization in initially amorphous oxides. This framework can guide the selection of growth and post-annealing conditions for Nb surfaces by narrowing the experimental parameter space, thereby reducing trial-and-error efforts in developing oxide structures relevant to SRF applications.

Tilkin, Anthony [Unlisted, US, IL; Fermilab]↗
DOE OSTI2021

On the planar limit of 3d $$ {\mathrm{T}}_{\rho}^{\sigma}\left[\mathrm{SU}\left(\mathrm{N}\right)\right] $$

A bstract We discuss a limit of 3d $$ {T}_{\rho}^{\sigma}\left[\mathrm{SU}(N)\right] $$ T ρ σ SU N quiver gauge theories in which the number of nodes is large and the ranks scale quadratically with the length of the quiver. The sphere free energies and topologically twisted indices are obtained using supersymmetric localization. Both scale quartically with the length of the quiver and quadratically with N , with trilogarithm functions depending on the quiver data as coefficients. The IR SCFTs have well-behaved supergravity duals in Type IIB, and the free energies match precisely with holographic results. Previously discussed theories with N 2 ln N scaling arise as limiting cases. Each balanced 3d quiver theory is linked to a 5d parent, whose matrix model is related and dominated by the same saddle point, leading to close relations between BPS observables.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Study of argon expulsion from the post-disruption runaway electron plateau following low-Z massive gas injection in DIII-D

Herein, a 1D radial diffusion model is developed to study the observed rapid expulsion of argon from the runaway electron plateau in the DIII-D tokamak following secondary massive low-Z (D 2 or He) gas injection. The expulsion of argon is found to be caused by further cooling of the background plasma due to the added neutrals, accompanied by recombination of argon ions and greatly increased outward radial transport rate of argon (now dominantly in neutral form) out of the runaway electron beam. After argon expulsion, power loss out of the runaway electron plateau is found to be dominated by neutral transport to the wall (rather than by radiation); this result resolves the power balance discrepancy highlighted in previous work on argon expulsion out of the runaway electron plateau.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Extrapolar Cloud Feedbacks as a Driver of Arctic Amplification

The role of cloud feedbacks in Arctic amplification (AA) of anthropogenic warming remains unclear. Traditional feedback analysis diagnoses the net cloud feedback as strongly positive in the tropics but either weak or negative in the Arctic, suggesting that AA would be amplified if cloud feedbacks were suppressed. However, in cloud-locking experiments using the slab ocean version of the Energy Exascale Earth System Model (E3SM), we find that suppressing cloud feedbacks results in a substantial decrease in AA under greenhouse gas forcing. We show that the increase in AA from cloud feedbacks arises from two main mechanisms: 1) the additional energy contributed by positive cloud feedbacks in the tropics leads to increased poleward moist atmospheric heat transport (AHT) which then amplifies Arctic warming; and 2) the additional Arctic warming is amplified by positive noncloud feedbacks in the region, together making extrapolar cloud feedbacks amplify AA. We also find that cloud changes can modify the strength of noncloud feedback, but that modification has a small effect on Arctic warming. We further examine the role of cloud feedbacks in AA using a moist energy balance model, which demonstrates that interactions of cloud feedbacks with moist AHT and other positive feedbacks dominate the influence of clouds on the pattern of surface warming. However, the contribution of cloud-induced changes in noncloud feedbacks on AA is relatively minor. Furthermore, these results demonstrate that traditional attributions of AA, that are based on local feedback analysis, overlook key interactions between extrapolar cloud changes, poleward AHT, and noncloud feedbacks in the Arctic.

58 GEOSCIENCES↗
DOE OSTI2024

Old-Aged groundwater contributes to mountain hillslope hydrologic dynamics

Understanding connectivity between the soil and deeper bedrock groundwater is needed to accurately predict a watershed’s response to perturbation, such as drought. Yet, the bedrock groundwater dynamics in mountainous environments are typically under-constrained and excluded from watershed hydrologic models. Here, we investigate the role of groundwater characterized with decadal and longer water ages on the hydrologic and mass-transport processes within a steep snow-dominated mountain hillslope in the Central Rocky Mountains (USA). We quantify subsurface and surface water mass-balance, groundwater flowpaths, and age distributions using the ParFlow-CLM integrated hydrologic and EcoSLIM particle tracking models, which are compared to hydrometric and environmental tracer observations. An ensemble of models with varied soil and hydrogeologic parameters reproduces observed groundwater levels and century-scale mean ages inferred from environmental tracers. The numerical models suggest soil water near the toe of the hillslope contains considerable (>60 % of the mass-flux) contributions from bedrock flowpaths characterized with water ages >10 years. Flowpath connectivity between the deeper bedrock and soil systems is present throughout the year, highlighting the potentially critical role of groundwater with old ages on processes such as evapotranspiration and streamflow generation. The coupled numerical model and groundwater age observations show the bedrock groundwater system influences the hillslope hydrodynamics and should be considered in mountain watershed conceptual and numerical models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Modeling Snow Dynamics and Stable Water Isotopes Across Mountain Landscapes

Abstract A coupled hydrologic and snowpack stable water isotope model assesses controls on isotopic inputs across a mountainous basin. Annually, the most depleted isotope conditions occur in the upper subalpine where snow accumulation is high, and rainfall is low. Snowmelt isotopic evolution over time indicates fractionation processes account for <25% snowmelt enrichment. Meltwater isotopic inputs are largely determined by controls on the amount, phase and isotopic mass of precipitation coincident with the ablation period. Effect of vapor loss from the snowpack on d‐excess in snowmelt is a balance between energy and snow‐availability. It is highest above treeline, and in the grass and aspen‐dominated portions of the upper montane where vegetation shading is low. Deep snowpack in conifer forests limit the influence of vapor loss in the subalpine. Wet years reduce the effects of vapor loss on snowmelt across the basin, except in the lower montane where added snowfall bolsters snow‐limited conditions.

58 GEOSCIENCES↗
DOE OSTI2021

Balancing Interfacial Reactions to Achieve Long Cycle Life in High Energy Lithium Metal Batteries

Rechargeable lithium (Li) metal batteries have attracted wide attentions as the next generation energy storage technologies. However, simultaneously achieving high cell-level energy density and long cycle life in realistic batteries is still a great challenge. Here we investigate the cell degradation mechanisms of Li||LiNi0.6Mn0.2Co0.2O2 pouch cells using different, but representative cell configurations to understand the fundamental linkage among Li thickness, electrolyte depletion and the structure evolution of solid electrolyte interphase (SEI) layers. Different cell failure modes were discovered when tuning the anode to cathode capacity (N/P) ratio in compatible electrolyte. With a thick-Li anode (N/P ratio = 2.5), initial stable cycling is obtained because of the abundant Li supply from the anode together with an artificially inflated high Coulombic Efficiency, followed by a premature sudden cell death appears due to the enrichment of “ineffective SEI” which does not participate in the electrochemical reactions but keep increasing cell impedance. The anode-free cell (N/P 0:1) displays a steady capacity decay because cathode Li loss dominates from the beginning to the end of cell cycle life. An optimized thin-Li (N/P 1:1) well balances the Li consumption rate with the impedance buildup by minimizing the growth of ineffective SEI layer, thus decelerates cell polarization increasing and extends cycling. Contrary to conventional wisdoms, long cycle life is observed by using ultra thin-Li (20 µm) in balanced cells. A prototype 350 Wh kg-1 pouch cell (2.0 Ah) achieves over 600 long stable cycles with 76% capacity retention without sudden cell death.

Niu, Chaojiang↗
DOE OSTI2020

Electron-Nanobunch-Width-Dominated Spectral Power Law for Relativistic Harmonic Generation from Ultrathin Foils

Relativistic high-order harmonic generation from solid-density plasma offers a compact source of coherent ultraviolet and x-ray light. For solid targets much thinner than the laser wavelength, the plasma thickness can be tuned to increase conversion efficiency; a reduction in total charge allows for balancing the laser and plasma driving forces, producing the most effective interaction. Unlike for semi-infinite plasma surfaces, in this study we find that for ultrathin foil targets the dominant factor in the emission spectral shape is the finite width of the electron nanobunches, leading to a power-law exponent of approximately 10/3. Ultrathin foils produce higher-efficiency frequency conversion than solid targets for moderately relativistic (1 0 <40) interactions and also provide unique insight into how the trajectories of individual electrons combine and interfere to generate reflected attosecond pulses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Enlarged Nonclosure of Surface Energy Balance With Increasing Atmospheric Instabilities Linked to Changes in Coherent Structures

The nonclosure of surface energy balance remains an outstanding problem in eddy covariance (EC) measurements of land-surface fluxes of heat, water vapor, and CO 2 . Our data collected from an EC tower over a semiarid sagebrush ecosystem indicate that under unstable atmospheric conditions, the nonclosure becomes increased with increasing instability, consistent with many other studies. It is demonstrated that the increased nonclosure is not caused by the inadequate sampling of large-scale turbulent motions using a 30-min averaging interval, though the scales of turbulent motions dominating sensible and latent heat fluxes become enlarged with increasing instability. Quadrant analysis is then used to reveal that the flux contributions from ejections remain nearly constant with increasing instability, whereas the flux contributions from sweeps are reduced and their time fractions increase. Our results imply that the increased nonclosure of surface energy balance is associated with changes in turbulent structures including their dominant time scales and flux contributions of ejections and sweeps as the atmospheric instability increases, which require further studies using vertically distributed observations and/or large eddy simulations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

The balance of orbital overlap and orbital energy in the activation of methane by actinide cations: insights from inductively coupled plasma tandem mass spectrometry

The actinides present a unique challenge to chemical theory. The classical view of covalent bonding is driven by the extent of spatial overlap of valence orbitals. Modern theory has expanded assessments of covalency to include considerations of orbital energy degeneracy to assess orbital energy mixing between metal and ligand valence orbitals. Actinide–ligand (An–L) bonding has more recently been described as a balance between orbital overlap and orbital energy mixing, where 5f and L valence orbital overlap decreases while energy mixing between An 5f and L valence orbitals increases across the series. To test these existing views, we employed inductively coupled plasma tandem mass spectrometry to examine the kinetic energy dependences of reactions of actinide cations, Th + –Am + , with methane. Further, this is the first experimental report of the energy dependences of methane activation reactions involving the cations of Pa, Np, Pu, and Am and the first experimental determination of transuranic An + –D, An + –CD 2 , An + –CD 3 , and An + –CD bond dissociation energies. The correlation of the measured An + –CD 2 bond energies with E p (6d 2 ) indicates that An + 6d orbitals are the dominant contributors in the An + –CD 2 bonds. Close examination of the relative reactivities of An + offers additional support that the balance of classical and modern views of molecular bonding may lie between Np + and Pu + and that the increased reactivity of Th + –Np + may be attributed to the increased spatial extension of the 5f orbitals whereas covalent An + bond formation may be more driven by the decreasing energies of the 5f orbitals across the actinide series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗